Certain thiolcarbamate compounds



United States Patent 3,330,821 CERTAIN TIHOLCARBAMATE COMPOUNDS Marlon W. Harman and John J. DAmico, Dunbar, W. Va, assiguors to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Continuation of applications Ser. No. 642,924 and Ser. No. 642,948, Feb. 28, 1957, and Ser. No. 853,988, Nov. 19, 1959. This application June 25, 1965, Ser. No. 467,085 Claims priority, application Sweden, May 6, 1959, 4,396/59 34 Claims. (Cl. 260-239) This application is a continuation of applications Ser. No. 642,924, filed Feb. 28, 1957, Ser. No. 642,948, filed Feb. 28, 1957, and Ser. No. 853,988, filed Nov. 19, 1959, and now abandoned.

This invention relates to new esters of thiolcarbamic acids and to methods for their preparation. These compounds possess biological activity and have other uses hereinafter illustrated. The invention includes methods of destroying or controlling undesired vegetation, fungi, and nematodes and relates to biologically active compositions useful for such purposes. More particularly it relates to methods of destroying or controlling undesired vegetation and other pests which comprises applying thereto an effective concentration of a toxic ester of a thiolcarbamic acid.

General objects of the invention are to provide esters of thiolcarbamic acids, methods for preparing them, and to provide compositions which are toxic to living plants, nematodes, fungi, or other pests or combinations thereof, and to provide methods for their use to accomplish various desirable ends. A further general object is to provide compositions and methods for the destruction of noxious vegetation. Another object is to provide defoliating compositions. Another object is to destroy noxious vegetation either in the form of germinating seeds or by application of the toxicant to the foliage after emergence. Still another object is to provide methods for destroying nematodes. A particular object of the invention is to provide outstanding grass-specific premergence herbicides and methods for using them. A further particular object is to provide methods for the destruction or control of grasses by applying the toxicant to the foliage and to provide compositions for such purpose. Still another particular object is to provide methods for the destruction or control of broadleaved plants and to provide herbicidal compositions for such purposes. A further particular object is to provide compositions which not only are toxic to plants but destroy or control fungi. Other and further objects will be apparent from the detailed description which follows.

The compounds conform to the structure where R is an organic amino substituent having the nitrogen atom connected directly to the carbon of the and to two other carbon atoms and where R represents a non-aromatic unsaturated radical. By non aromatic is meant that a carbon atom which is part of an aromatic ring is not connected directly to the sulfur. The valences of the amino substituent represented by R are preferably satisfied by lower alkyl groups but if the chain is interrupted by oxygen or sulfur, compounds having higher molecular weights maintain high biological activity. Moreover, heterocyclic amino substituents are especially efiicacious. The unsaturated group represented by R is prefer- 3,330,821 Patented July 1 1, 1967 ably an alkenyl group either unsubstituted or substituted by halogen although the presence of halogen serves significantly to support the biological activity. Typical examples of R comprise cisand trans-2,3-dichloro-2-butenyl, 3-chloro -2 -butenyl, 2-chloroallyl, 2-bromoallyl, 3-chloroallyl, cisand trans-2,3-dichloroallyl, 3-iodoallyl, 3-iodo-2-butenyl, 2,3-diodo-2-butenyl, 2-fluoro-3-chloroallyl, vinyl, allyl, 2-butenyl, 4-chloro-2-butenyl, 2-iodoallyl, 3-bromoal1yl, and 2,3-dibromoallyl.

Cyclohexeuyl esters are desirable but aromatic and saturated esters are not included.

Several methods are available for the preparation of thiolcarbamate esters. The halide corresponding to the desired ester is condenser with an alkali metal thiolcarbamate in one method. The alkali metal thiolcarbamates are available from reaction of carbonoxysulfide with amines in the presence of alkali. In another method a thionocarbamate ester is rearranged to a thiol ester by reaction with an alkyl halide. The rearrangement is accompanied by trans esterification. Still another method is to condense a carbonyl halide with a mercaptan or mercaptide.

Example I thiolcarbamate solution so prepared there wasadded with stirring 36.2 grams (0.25 mole) of cisand trans-1,2,3- tn'chloro-l-propene, the stirring continued at 25 -30 C. for 24 hours, then the mixture heated at 5060 C. for 3 hours. After cooling to 20 C. the reaction mixture was extracted with 300 ml. of ethyl ether, the ether solution washed with water until the washings were neutral to litmus, dried over sodium sulfate and the ether removed in vacuo at a maximum temperature of 90 C./12 mm. The cisand trans-2,3-dichloroallyl dimethylthiolcarbamate, an amber oil, was obtained in 65% theory yield. Analysis gave 33.02% chlorine as compared to 33.11% calculated for C H Cl NOS.

Example 2 Employing a quantity of the same sodium dimethylthiolcarbamate solution in the same proportion and under the same reaction conditions but replacing the cisand trans-1,2,3-trichloro-l-propene by 19.1 grams (0.25 mole) of allyl chloride, allyl dimethylthiolcarbamate was obtained as an amber oil in 60.6% yield. Analysis gave 9.50% nitrogen and 22.30% sulfur as compared to 9.65% nitrogen and 22.07% sulfur calculated for C H NOS.

Example 3 In the procedure of Example 1 and utilizing another portion of the same alkali metal thiolcarbamate, 27.8 grams (0.25 mole) of 2,3-dichloro-l-propene was substituted for the cisand trans-1,2,3-trichloro-l-propene. The 2-chloroallyl dimethylthiolcarbamate was obtained as an amber oil, B.P. 112-114 C./4 mm. Analysis gave 7.35% nitrogen and 18.11% sulfur as compared to 7.80% nitrogen and 17.84% sulfur calculated for C H CINOS.

The same compound was prepared from ethyl dimethylthionocarbamate. To 133.2 grams (1.0 mole) of ethyl dirnethylthionocarbamate was added with stirring 150 grams (1.35 moles) of 2,3-dichloro-1-propene. The stirred reaction mixture was heated at 115 C. for 48 hours and then distilled to yield 2-chl0roallyl dimethylthiolcar- 3 bamate, B.P. 112ll3 C./4 mm., in 46.9% yield. Analysis gave 7.78% nitrogen and 17.68% sulfur as compared to 7.80% nitrogen and 17.84% sulfur calculated for C H CLNOS.

Example 4 To a stirred solution comprising 180 grams (1.0 mole) of 25% dimethylamine, 160 grams (1.0 mole) of 25% sodium hydroxide and 1000 ml. of Water there was bubbled in carbonxysulfide at -5 C. until there was a gain in weight of 75 grams (1.25 moles). The solution was stirred for an additional hour at room temperature and to this solution 145.3 grams (1.0 mole) of 1,1,3-trichloro-l-propene was added in one portion. Stirring was continued for 24 hours at room temperature and the reaction mixture extracted with 500 ml. of ethyl ether. The ether solution was washed with water until neutral to litmus, dried over sodium sulfate, and the ether removed in vacuo. Distillation of the reaction mixture under 4 mm. pressure gave an amber oil, B.P. l38140 C. The 3,3- dichloroallyl dimethylthiolcarbamate so obtained analyzed 6.54% nitrogen and 14.45% sulfur as compared to 6.54% nitrogen and 14.98% sulfur calculated for C H CI NOS.

Example A 12.7% aqueous solution of sodium diethylthiolcarbamate was prepared by mixing 146.3 grams (2.0 moles) of diethylamine, 320 grams (2.0 moles) of 25% sodium hydroxide and 2000 ml. of water. To this solution, with stirring at 0 C., there was bubbled in carbonoxysulfide until the gain in weight was 146 grams. The solution was stirred for an additional 2 hours at 0-5 C.

To 412.5 grams (0.33 mole) of the sodium diethylthiolcarbamate solution so prepared there was added in one portion with stirring 36.4 grams (0.25 mole) of 1,1,3- trichloro-l-propene. The stirred mixture was heated at 5060 C. for 3 hours and then maintained at 2530 C. for 12. hours. The product was extracted with 300 ml. of ethyl ether, the ether solution washed with water until neutral to litmus, and dried over sodium sulfate. The ether was removed in vacuo at a maximum temperature of 80-90 C./1-2 mm. The 3,3-dich1or-oallyl diethylthiolcarbamate so obtained was an amber oil, Analysis gave 5.79% nitrogen, 13.25% sulfur and 29.95% chlorine as compared to 5.78% nitrogen, 13.24% sulfur and 29.28% chlorine calculated for C H CI NOS.

Employing a quantity of the same sodium diethylthiolcarbamate as prepared in Example 5 and proceeding as in Example 5, the following compounds were prepared:

Example 6 Cisand trans-2,3-dichloroallyl diethylthiolcarbamate was obtained in 84.5% yield from cisand trans-1,2,3- trichloropropene. The product was an amber oil analyzing 5.59% nitrogen, 13.05% sulfur, and 29.61% chlorine as compared to 5.78% nitrogen, 13.20% sulfur, and 29.20% chlorine calculated for C H C1 NOS.

Example 7 Allyl diethylthiolcarbamate was obtained in 95% yield from allyl chloride. The product was an amber oil analyzing 8.03% nitrogen and 18.43% sulfur as compared to 8.08% nitrogen and 18.50% sulfur calculated for C H NOS.

Example 8 2-bromoallyl diethylthiolcarbamate was obtained in 89% yield from 2,3-dibromo-1-propene. The product was an amber oil analyzing 5.43% nitrogen and 31.40% bromine as compared to 4.54% nitrogen and 31.65% bromine calculated for CBHMBI'NOS.

Example 9 2-chloroallyl diethylthiolcarbamate was obtained in 83% yield from 2,3-dichloro-1-propene. The product was an amber oil analyzing 6.94% nitrogen and 15.78% sulfur as compared to 6.74% nitrogen and 15.44% sulfur calculated for C H ClNOS.

Example 10 To a stirred solution of 202.4 grams (2.0 moles) of din-propylamine in 1000 ml. of dry ethyl ether at -10 to 0 C. there was bubbled in carbonoxysulfide until the gain in weight was grams. This addition required 30 minutes and the mixture was then stirred at -10 to 0 C. for an additional 90 minutes. Thereupon 111 grams (1.0 mole) of 2,3-dichloro-1-propene was added in one portion and the reaction mixture stirred at 25 -30 C, for 24 hours. The by-product salt was removed by filtration and the excess ether removed in vacuo. The residue was distilled in vacuo and the fraction boiling at 148 -149 C./8 mm. collected. The 2-chloroallyl di-n-propylthiolcarbamate was an amber liquid analyzing 5.63% nitrogen as compared to 5.94% calculated for C H ClNOS.

Example 11 In the procedure of Example 10, 139 grams (1.38 moles) of di-n-propylamine in 500 ml. of dry ether, 90 grams (1.5 moles) of carbonoxysulfide and 53 grams (0.69 mole) of allyl chloride were employed as reactants. The allyl di-n-propylthioloarbamate, B.P. 132 C./12 mm., was obtained in 52.7% yield analyzing 6.68% nitrogen as compared to 6.96% calculated for C H NOS.

Example 12 To a stirred solution of 202.4 grams (2.0 moles) of diisopropylamine in 1000 ml. of dry ethyl ether at 10 to 0 C. there was bubbled in carbonoxysulfide until the gain in weight was 120 grams. This addition required 30 minutes and the mixture was then stirred at l0 to 0 C. for an additional 90 minutes. Thereupon 145.4 grams (1.0 mole) of 1,2,3-trichloropropene was added in one portion and the reaction mixture stirred at 2530 C. for 24 hours. The by-product salt was removed by filtration and the excess ether removed in vacuo. The residue was distilled in vacuo and the fraction boiling at l59 C./9 mm. collected. The cisand trans-2,3-dichloroallyl diisopropylthiolcarbamate was an amber liquid analyzing 11.83% sulfur as compared to 11.87% calculated for C I-I CI NOS.

The same product was readily prepared in aqueous medium by bubbling 76.5 grams (1.1 moles) of 85% carbonoxysulfide into a mixture of 105 grams of 97% diisopropylamine, 200 ml. of water and grams of 25% sodium hydroxide at 26 C. There was then added 145.5 grams of 1,2,3-t-richloropropene in one portion. The temperature was kept below 12 C. for about an hour by cooling with an ice bath. The ice bath was then removed. The temperature rose slowly to 30 C. in 4 hours. 400 ml. of water was added, the organic layer separated, washed with water and stripped at 95 100 C./ 14 mm, The residue was then distilled, collecting the fraction boiling at 118-119 C./1mm.

Example 13 Employing 196 grams (2.0 moles) of diallyamine in 1000 ml. of ether, 77 grams (1.29 moles) of carbonoxysulfide and 111 grams (1.0 moles) of 2,3-dichloro-1- propene and following the procedure of Example 10, 2- chloroallyl diallylthiolcarbamate, B.P. 142l43 C./9 mm., was obtained as an amber liquid. Analysis gave 5.86% nitrogen as compared to 6.04% calculated for C H ClNOS.

Example 14 Trans-2,3-dich1oroallyl diisopropylthiolcarbamate was prepared by the following procedure: To a solution of 56.5 grams (0.5 mole) of 88% diisopropylamine, 100 ml. of water and 80 grams of 25% sodium hydroxide at 0- 5 C. was added 38 grams (0.55 mole) of 85% carbonoxysulfide. This was followed by adding dropwise at 0- 5" C. 72.7 grams (0.5 mole) of trans-1,2,3-trichloropropene, B.P. 134135 C. Stirring was continued 1 hour at C. and then over a period of 4 hours the temperature was raised to 27 C. Water, 200 ml., was added, the organic layer separated, washed with water and stripped at 100 C./ 14 mm. The pure ester distilled at 16016l C. at 10 mm. Hg.

Example 15 Substituting cis-1,2,3-trichloropropene, B.P. 148.5 C., in the foregoing procedure yielded cis-2,3,-dichloroallyl diisopropylthiolcarbamate as a yellow oil, B.P. 164.5 165 C./l0 mm., M.P. 3840 C.

Example 16 To a cold stirred solution of 33.4 grams (0.25 mole) of 2-chloro-N-isopropylallylamine and 40 grams (0.25 mole) of 25% sodium hydroxide in 50 ml. of water there was bubbled in at -10 C. carbonoxysulfide until the gain in weight was 19.5 grams. After this addition, which required an hour, there was added in one portion 36.2 grams (0.25 mole) of cisand trans-1,2,3-trichloropropene. Stirring was continued for 5 hours at 25 -30 C. and the reaction mixture then extracted with 400 ml. of ethyl ether and filtered to remove by-product salt. The ether solution was washed with water until neutral to litmus, dried over sodium sulfate and the ether removed in vacuo at a maximum temperature of 80-90 C./12 mm. The cisand trans-2,3-dichloroallyl N-(2-chloroallyl)isopropylthiolcarbamate so obtained was an amber liquid analyzing 4.3% nitrogen as compared to 4.6 calculated for C H CI NOS.

Example 17 Substituting 33.3 grams (0.25 mole) of 2,2'-dimethoxy diethylamine for the 2-chloro-N-isopropyla1lylamine in the procedure of Example 14, cisand trans-2,3-dichloroallyl bis(Z-methoxyethyl)thiolcarbamate was obtained as an amber liquid analyzing 4.2% nitrogen as compared to 4.6% calculated for C H Cl O S.

Example 18 A solution comprising 21.5 grams (0.25 mole) of piperazine, 80 grams (0.5 mole) of 25% sodium hydroxide and 50 ml. of water was prepared and 85% carbonoxysulfide then bubbled in at 510 C. for approximately an hour or until the gain in weight was 39 grams. Thereupon there was added in one portion 72.5 grams (0.5 mole) of cisand trans-1,2,3-trichloropropene and stirring continued for 5 hours at 25 30 C. The reaction mixture was then diluted with 400 ml. of water, the solution extracted with 400 ml. of ethyl ether and the byproduct salt removed by filtration. The ether solution was Washed with water until neutral to litmus, dried over sodium sulfate and the ether removed in vacuo at a maximum temperature of 80-90 C./l2 mm. The bis(cisand trans-2,3-dichloroallyl) 1,4-piperazinedi carbothiolate was an amber liquid analyzing 6.2% nitrogen as compared to 6.6% calculated for C H CMN O S Example 19 To a stirred solution of 35.3 grams (0.25 mole) of N-ethylaniline, 50 ml. of ethyl alcohol and 16.5 grams (0.25 mole) of 85 potassium hydroxide at 0 C. there was bubbled in 19.5 grams (0.275 mole) of 85% carbonoxysulfide. The addition was made at 0-10 C. over about an hour. To the resulting slurry at 5 C. was added 36.3 grams (0.25 mole) of 1,2,3-trichloropropene in one portion. The reaction mixture was stirred at 0-10 C. for half an hour and then at 25 -30 C. for 5 hours. After adding 300 ml. of water and 300 ml. of ethyl ether, the reaction mixture was stirred for minutes, then the ether layer separated and washed with dilute hydrochloric acid until neutralization of the wash water gave no turbidity. The ether layer was then washed with water until neutral to litmus, dried over sodium sulfate and the ether removed in vacuo at a maximum temperature of -90 C. at 1-2 mm. The product, 2,3-dichloroallyl N-ethylthiolcarbanilate, was an amber oil.

Example 20 To a stirred solution of 31.8 grams (0.25 mole) of N-ethylcyclohexylamine, 50 ml. of water and 40 grams (0.25 mole) of 25% sodium hydroxide at 05 C. was added 19.5 grams (0.275 mole) of carbonoxysulfide. There was then added in one portion 36.7 grams (0.25 mole) of 1,2,3-trichloropropene. Stirring was continued at 05 C. for 1 hour and thenover a period of 4 hours the temperature was raised to 30 C. The product was extracted with 400 ml. of ethyl ether, the ether solution washed with water until neutral to litmus and dried over sodium sulfate. The ether was removed in vacuo at a maximum temperature of 8090 C./12 mm. The cis and trans-2,3 dichloroallyl N-ethyl-N-cyclohexylth iolcarbamate was-an amber oil analyzing 4.53% nitrogen and 23.37% chlorine as compared to 4.73% nitrogen and 23.94% chlorine calculated for C H Cl NOS.

Other typical toxicants obtainable by similar procedures are recorded below. These are merely cited further to illustrate the invention and variations will be evident to those skilled in the art. For the most part, the products are amber oils. cisand trans-2,3-dichlorallyl N-butyl-N- cyclohexylthiolcarbamate, however, was an amber semisolid. This compound was a selective crabgrass killer. Any of these compounds or mixtures thereof are efiective when used as described to destroy or control undesired vegetation:

3-chloro-2-butenyl dimethylthiolcarbamate 3-chloro-2-butenyl diethylthiolcarbamate 3-chloroallyl diethylthiolcarbamate 3-ch1oroa1lyl dimethylthiolcarbamate 3-chloro-2-butenyl-4-morpholinecarbothioate 2-chloroallyl-4-morpholinecarbothioate 3-chlor0allyl-4-morpholinecarbothioate 3-chloro-2-butenyl diallylthiolcarbamate 3-chloroallyl diallylthiolcarbamate 2-chloroallyl dibutylthiolcarbamate 3-chloroallyl dibutylthiolcarbamate 3-chloroally1 diisopropylthiolcarbamate 3-chloro-2-butenyl diisopropylthiolcarbamate 3-chloroallyl N-(fi-cyanoethyl)-N-isopropylthio1carbamate 3-chloro-2-butenyl dipropylthiolcarbamate 2-chloroallyl N-(allyl)isopropylthiolcarbamate 3-chloro-2-butenyl N-(allyl)isopropylthiolcarbamate 2-chloroa1lyl N-(Z-chloroallyl) isopropylthiolcarbamate 3-chloroallyl N-(2-chloroallyl)isopropylthiolcarbamate 2-chloroallyl diisobutylthiolcarbamate 3-chloroallyl-1-pyrrolidinecarbothioate 2-chloroallyl-1-pyrrolidinecarbothioate 3-chloro-2-butenyl-1-pyrrolidinecarbothioate cisand trans-2,3-dichloroallyl diallylthiolcarbamate 2-bromoallyl diisopropylthiolcarbamate 2-bromoallyl diallylthiolcarbamate 2-bromoallyl N-(2-chloroallyl)isopropylthiolcarbamate allyl N-(Z-chloroallyl)isopropylthiolcarbamate allyl N-(2-ch1oroallyl)-3-methoxypropylthiolcarbamate allyl N-(fi-cyanoethyl)-N-isopropylthiolcarbamate allyl N-(allyl)isopropylthiolcarbamate allyl diisopropylthiolcarbamate allyl diallylthiolcarbamate allyl dibutylthiolcarbamate cisand trans-2,3-dichloroallyl N-(allyl)isopropylthiolcarbamate cisand trans-2,3-dichloroallyl N-(2-chloroallyl)isopropylthiolcarbamate allyl 4-phenyl-1-piperazinecarbothioate 3-chloro-2-fluoroallyl diisopropylthiolcarbamate 2-bromoallyl allylisopropylthiolcarbamate 2-bromoallyl 4-phenyl-l-piperazinecarbothioate trans-2,3-dichloroallyl diethylthiolcarbamate cis-2,3-dichloroallyl diethylthiolcarbamate 3,3-dichloroallyl diisopropylthiolcarbamate trans-2,3-dichloro-2-butenyl diisopropylthiolcarbamate trans-2,3-dichloro-2-butenyl diethylthiolcarbamate 2-chloroallyl bis(2-methoxyethyl)thiolcarbamate allyl bis(Z-methoxyethyl)thiolcarbamate 3,3-dichloroallyl bis(2-methoxyethyl)thiolcarbamate 2-chloroallyl bis( Z-methoxypropyl) thiolcarbamate 3.3-dichloroallyl l-pyrrolidinecarbothioate allyl 1-pyrrolidinecarbothioate, allyl l-pineridinecarbothioate 2-chloroallyl l-peperidinecarbothioate 3.3-dichloroallyl l-piperidinecarbothioate 3-chloro-2-butenyl l-piperidinecarbothioate 2-chloroallyl Z-methyl-l-piperidinecarbothioate 2-chloroallyl bis- Z-phenoxyethyl thiolcarb amate 2-chloroallyl N-2-phenoxyethyl-N-ethylthiolcarbamate 2-chloroallyl bis- Z-benzyloxyethyl thiolcarb amate 2-chloroallyl N-2-benzyloxyethyl-N-ethylthiolcarbamate 2-chloroallyl N-cyclohexyl-N-ethylthiolcarbamate vinyl dibutylthiolcarbamate methallyl diethylthiolcarbamate 2-cyclohexenyl diethylthiolcarbamate 2-chloroallyl-5-ethyl-3-methyl-l-piperidinecarbothioate 2-chloroallyl N-(methyl)cyclohexenylthiolcarbamate It will be noted that the examples illustrate compounds in which the amino substituent R of the general formula contains 2 to 18 carbon atoms, inclusive, and that these amino substituents include saturated monoamino-hydrocarbon radicals of 2 to 8 carbon atoms, bis(hydrocarbonoxyloweralkyl) amino in which any unsaturation is aromatic, bis(lower 2-alkenyl) amino and unsymmetrically disubstituted amino where one substituent is selected from a group consisting of lower 2-alkenyl, chlorolower- 2-alkenyl, cyanoloweralkyl, hydrocarbonoxyloweralkyl in which any unsaturation is aromatic and cyclohexenyl and the other is a different member of the group consisting of loweralkyl and hydrocarbonoxyloweralkyl in which any unsautration is aromatic.

Further examples of biologically active thiolcarbamates comprise the following:

cisand trans-2,3-dichloroallyl S-ethyl-Z-methylpiperidinocarbothiolate cisand trans-2,3-dichloroallyl N-butyl N-cyclohexylthiolcarbamate cisand trans-2,3-dichloroallyl N-cyclohexyl-N-allylthiolcarbamate 2,3,3-trichloroallyl N-cyclohexyl-N-isopropylthiolcarbamate cisand trans-2,3-dichloroallyl N-ethyl-N-(4-methylcyclohexylthiolcarbamate 2,3,3-trichloroallyl dimethoxypropylthiolcarbamate 2,3,3-trichloroally1 dibutylthiolcarbamate 2,3,3-trichloroallyl l-pyrrolidinecarbothiolate 2,3,3-trichloroallyl N-tetrahydrofurfuryl N-propylthiolcarbamate 2,3,3-trichloroallyl N-tetrahydrofurfuryl N-ethylthiolcarbamate 2,3,3-trichloroallyl N-furfuryl-N-methylthiolcarbamate 2,3,3-trichloroallyl diisobutylthiolcarbamate 3,4,4-trifluoro-3-butenyl diisopropylthiolcarbamate cisand trans-2,3-dichloroallyl-4-morpholinecarbothiolate cisand trans-2,3-dichloroallyl N-(2-cyanoethyl)-N-isopropylthiolcarbamate cisand trans-2,3-dichloroallyl N-(2-phenoxyethyl)-N- methylthiolcarbamate cisand trans-2,3-dichloroallyl N-Z-benzyloxyethyl-N- methylthiolcarbamate cisand trans-2,3-dichloroallyl N-dodecyl-N-methylthiolcarbamate cisand trans-2,3-dichloroallyl N-octyl-N-methylthiolcarbamate cisand trans-2,3-dichlorallyl N-methyl-N-cyclopentylthiolcarbamate cisand trans-2,3-dichloroallyl N-methyl-N-cyclooctylthiolcarbamate cisand trans-2,3-dichloroallyl l-hexamethyleniminecarbothiolate 2,3,3-trichloroallyl 1-hexamethyleniminecarbothiolate cisand trans-2,3-dichloroallyl di(ethoxyethyl)thiolcarbamate The phytotoxic esters of thiolcarbamic acids comprise weed killers having both pre-emergence and post-emergence activity. Accordingly, by applying the toxicant to the plant is meant any means whereby the toxicant is brought into contact with living plants which latter include germinating seedlings, as for example by application to the ground before the plants emerge or by direct application to the foliage. The thiolcarbamate herbicides are effective against a wide variety of plants including grasses and broadleaved plants. Some of them are outstanding grass specific pre-emergence herbicides. They also include defoliants and nematocides.

The discovery of compounds toxic to broadleaf plants but relatively innocuous to grasses has created considerable demand for compounds to destroy undesired grasses. It is therefore significant that thiolcarbamates were discovered which posses this property. Outstanding examples comprise Z-chloroallyl dimethylthiolcarbamate, cisand trans-2,3-dichloroallyl dimethylthiolcarbamate, cisand trans-2,3-dichloroallyl diethylthiolcarbamate, 2-brornoallyl diethylthiolcarbamate, 3,3-dichloroallyl diethylthiolcarbamate, 2-choroallyl diethylthiolcarbamate, 3,3-dichloroallyl dimethylthiolcarbamate, and allyl diethylthiolcarbamate.

The new toxicants may be applied conveniently in the form of a spray containing the active ingredient in a concentration within the range of 0.1%-10.0% by weight. Thorough coverage of the foliage is effective for contact killing. For pre-emergence control of grasses, amounts within the range of A1-60 pounds per acre have been used successfully. Examples of grasses which are controlled are foxtail, cheat grass, wild oats, rye grass, and crab grass. Weeds from the following plant familes are controlled to varying degrees: Leguminaseae, Cucurbitaceae, Umbellifererae, Chenopodiaceae, Amarenthaceae, Convolvulaceae, and Aizoaceae. At concentrations within the range of 35-100 pounds per acre the new compounds are soil sterilants and destroy all plant life as well as destroying some animal pests.

Although most thiolcarbamates are insoluble in water, they are soluble in organic solvents. Most of them are soluble in acetone, chloroform, ethyl alcohol, ethyl acetate, benzene, ether, and heptane. The esters may be dispersed directly in Water or a solution in an organic solvent emulsified in aqueous medium by the aid of a dispersing agent. As dispersing and wetting agents there may be employed soft or hard sodium or potassium soaps, alkylated aromatic sodium sulfonates such as sodium dodecyl benzene sulfonate, or an amine salt or dodecyl benzene sulfonic acid, alkali metal salts of sulfated fatty alcohols, ethylene oxide condensation products of alkyl phenols or tall oil and other dispersing and wetting agents.

The tables below illustrate characteristic herbicidal activity of typical thiolcarbamates. The toxicant was emulsified in Water and the emulsion applied as a spray. In the foliage application the spray containing the concentration of the active ingredient shown in the table was applied to the foliage of grass and to the foliage of bean plants and finally to the foliage of a mixture of broadleaved plants and the effect recorded. In the preemergence application the spray was applied to the attached to nitrogen, the second nitrogen substituent should preferably not be halogen-substituted alkenyl.

While the alkyl thiolcarbamates examined had only a low order of activity, the unsaturated esters proved to be 12 wetting agents, or emulsifying agents comprise morpholine or dimethylamine oleate, sulfonated fish, castor, and petroleum oils, sodium salt of lignin sulfonic acid, butyl or other amine salt of decyl or dodecylbenzene sulfonic very valuable compounds. Cyclic groups as for example acid, sodium lauryl sulfate, disodium monolauryl phoscyclohexenyl are desirable but aromatic esters are not phate, ethylene oxide condensation products of higher included. Thiazolyl esters, as for example 5-acetyl-4- alcohols or higher mercaptans. Mixtures of two or more methyl-Z-thiaz-olyl diethylthiolcarbamate, are useful, these surface-active agents are also feasible. Generally, the compounds being characterized by contact phytotoxicity surface-active agent will comprise only a small proporto broadleaves. tion of the composition, say 0.1- by weight of the The invention relates to plurally halogenated unsatuester. Solutions of the esters in organic solvents containrated thiolcarbamates. More particularly, it relates t ing small amounts of surface-active agent provide versatile methods of destroying or controlllng undesired vegeta herbicidal compositions useful either for direct applicatron which comprises applying thereto a tox c plurally tion to foilage and soil or for preparing aqueous sprays. h n t n r d ester a thwlcarbamlc acld- 15 A suitable formulation comprises 45 parts by weight heavy The blologlcany active Compounds Conform to the aromatic naphtha, 5 parts by weight organic surfacetruCtHI active agent, and 50 parts by weight ester toxicant.

The formulation of dry compositions for application ll as dusts or for further dilution with liquid carriers is RCSR readily accomplish by mlxing the ester with a finely where R 1s an orgamc ammo substituent having the nitrodivided Carrier. The latter will usually be in major gen atom connected dlrectly to the carbon the portions. Suitable carriers comprise talc, clay, pyrophyl- O lite, silica, fullers earth, diatomaceous earth, and flours H such as walnut shell, wheat, soya bean and cottonseed C flours. Magnesium or calcium carbonate and calcium phosphate are suitable solid carriers. Adsorption on inert g i g z gt g ig gfi gz i ggg fi gii i gf ggz granules such as granular forms of fullers earth provide g g effective forms more convenient to apply and use than radical having more than one halogen substituent. Typrdusts i examples of R .compnse lower anfenyl as follows: As illustrative of the herbicidal activity the ester was 015- and trans-2,3-d1chloro-2-butenyl, as and trans-2,3-

issolved in a relatlvely high volume of volatlle organic dichl-oroallyl, 2,3-d11odo-2-butenyl, 2-fiuoro-3-chloroallyl,

solvent and applied as a spray. In the follage application 2,3-d1bromoallyl, 3,4,4-tr1fluoro-3-butenyl, and 2,3,3-tr1- th e spray containing the active ingredient was applled chloroallyl. Outstanding examples comprise 2,3-d1chlorot o the foliage of grass and to the foliage of bean plants allyl d11sopropylthiolcarbamate, 2,3,3-tr1chloroallyl d1- and finally to the foliage of a mixture of broadleaved ethylthiolcarbamate, 2,3,3-tr1chloroallyl dnsopropylthiol- 1 d h ff d d I h h pants an t e e ect recor e n t e pie-emergence apcarbamate, and ClS- and trans 2,3 dichloroallyl N met y 1 p ication a counted number of seeds of various grasses N-cyclohexylth1olcarbamate.

and broadleaf plants were scattered on the 5011 surface The toxicants of the 1nvent1on are for the most part and covered with SO11. The soil was then sprayed with mobile 0115 and may be applied full strength in the form 4 th e volatile organic solvent contamlng the test chem1cal. of a spray but preferably in con unction with a herbicldal Ab out fourteen days after application of the toxlcants, ad uVant as carrier containing the active ingredient in a results were observed and recorded Th numbe f concentration within the range of about 0.l%50.0% by Seeds emer in was converted t Wei m f rbicidalr 5 weight. Although most thiolcarbamates are insoluble in in S basedgong avera e ercento ermgnatio an water, they may be dispersed therein and applied as aqueticgular Seed lot ou sprays. Most thiolcarbamates are soluble in acetone, re ularities of rafn s O i 1 h 3 l 6 chloroform, ethyl acetate, benzene, ether, and heptane. elimination f. n 53 g z l i Petroleum fractions make satisfactory, economical herbii m t t 85% t r 0 i f 9: cidal adjuvants and readily lend themselves to emulsificag s g i oxlclg tion in water where that is desired. Thorough coverage of and 5 3 sf ggi i g p '2 W z foliage is desirable for contact killing. For pre-emergent H rbiddal ratinl wer d We 8 i i i control of grasses, amounts within the range of /1360 e 1 e asslgne y means 0 e O pounds per acre have been used successfully. mg conve Slon Sea Whether applied in conjunction with a carrier or not, Percent emergency: Phytotoxicity rating admixture with a small amount of an organic surface- 0-25 3 or severe. active agent capable of lowering the surface tension of 26-50 2 or moderate. water is desirable for field application. Examples of sur- 51-75 1 or slight. face-active agents variously known as dispersing agents, 76-100 0 or none.

TABLE IIL-CONTACT Ph t t it B t Toxic-ant Cone,t y 0 0X10 y a mg percen Grass Bean Broadleaf 10 Cisband ttrans-2,8-dichloroallyl diisopropylthiol- 0 5 3 1 11 rfifsfhtenaanry'iassastagatrratnstaa:1: 0 5 3 1 5 12 Cis-2,3-dichloroallyldiisopropylthiolcarbamate 0 5 3 0 0 13 Cisand trans-2,3-dichloroallyl 5-ethyl-2-methylpiperidinecarbothiolate 0 5 1 1 1 14 Cisand trans-2,3-dichloroallyl N-2-ehlor0allyl N- isopropylthiolcarbamate 0 5 2 2 2 13 The plants employed in the pre-emergence application are designated by letter in Table IV. The plants corresponding to the letters are as follows:

Furthermore, incorporation into the top soil improves performance four-to-eightfold. For example, cisand trans-2,3 dichloroallyl diisopropylthiolcarbomate was mixed into the top layer of soil seeded to wild oats. At rates of A3 and pound per acre, the phytotoxicity ratings were 3 and 2 respectively in the greenhouse. More extensive tests in the field were carried out at four different locations where wild oats were a serious problem. In every case this toxicant was 99%l00% effective against wild oats in pre-emergent application at 1% pounds per acre when incorporated into the top soil at depths of 2-4 inches. At rates of four pounds per acre and above, this compound effectively controlled wild oats and some other weedy grasses when applied as a foliage spray to seedlings up to two weeks old. A high degree of eifectiveness was coupled with a relatively large safety factor. Muskmelon, tomato, sugar beets, alfalfa, peas, turnip, cotton, soybeans, snapbeans, corn, flax, and barley TABLE IV.PRE-EMERGENCE Toxicant No. Rate, Lbs. A B C D E F G H J K L M N O P per Acre 1 Cisand trans-2,3-diehloroallyl N-ethylthiolcarbanilate. 2 Cisand trans-2,3-dichloroallyl di(2-methoxyethyl)thiolcarbamate. Bis(eisand trans-2,3-dlel1l0roallyl)-1,4-piperazinediearbothiolate.

As these data indicate, the new toxicants are extremely effective, highly specific pre-emergent grass killers. The excellent wild-oat control is especially important in view of the magnitude of the wild-oat-control problem throughout the world. For elimination of this pest the presence of more than one halogen is important as evidenced by the following comparative data:

were resistant to the toxicant. Wheat was resistant, too, but the safety factor was lower. While the toxicants are primarily grass-specific herbicides, pigweed, plantain, and ragweed were fairly susceptible.

Table V illustrates the pre-emergent herbicidal activity of other typical compounds. The toxicants employed were as follows:

No. l8-2,3,3-trichloroallyl diallylthiolcarbamate Toxicit to Wild oats No. 192,3,3-trichloroallyldipropylthiolcarbarnate Y at Surface applwatlon No. 202,3,3-tr1chloroallyl N-cyclohexyl-N-ethylthiolcarrate ofbamate %po an d M pound No. 212,3,3-tr1chloroallyl dimethylthrolcarbamate per acre per acre The active ingredient was applied at a dosage of 25 pounds per acre to the soil of seeded plots before the grass 1 1 Or other plants emerged. The letters and the numerical thlolcarbamate 3 3 symbols have the same significance as in the preceding tables.

TABLE V ToxicantNo. ABQDEF'JLIOIP Table VI illustrates pre-emergent herbical activity of typical compounds at five pounds per acre. The toxicants employed were:

to destroy it by one means or another. To accomplish this result, it is necessary that the toxicant resist the destructive action of soil bacteria, be capable of wetting or penetrating the parasite, possess a substantial water dispersibility, be capable of ready mixture with the soil and possess a sufficiently low vapor pressure so that it does not eva orate before its destructive action is accomplished. Since the extracting requirements of any practical agent cannot be recognized by methods other than by test, it is necessary to observe the effectiveness of chosen compounds against the life cycle of the parasite.

Nematocidal activity was demonstrated by preparing a suspension of the nematode Panagrellus redivivus in water and observing through a microscope the motility of the organisms in the presence of 0.1% of the test material. The nematode in aqueous suspension will flex its body at a regular rate and as the nematocide takes effect, the rate TABLE VI TcxicantNo. A B C l D l E i F 11L 0 P Further to illustrate the increased effectiveness by inof flexing is decreased until death of the parasite occurs. corporating the toxicant into the top soil, the toxicants In this experiment the control containing no added toxilisted in Table VI were mixed into the top layer of soil cant showed undiminished activity after 24 hours whereseeded to wild oats. At a rate of /2 pound per acre, the as complete destruction of the nematode was effected with phytotoxicity rating was 3 in every case. At a rate of Z-chloroallyl dimethylthiolcarbamate and 2,3-dichloropound per acre, the phytotoxity rating was 3 for Toxicant allyl dimethylthiolcarbamate. Although less effective, ac N0. 24 and Toxicant No. 29 was completely effective at tivity as contact nematocides was exhibited by 3,3-dichl0- pound per acre. roallyl diethylthiolcarbamate, 2,3-dichloroallyl diethyl As explained above, the compounds contemplated here thiolcarbamate, 2-bromoallyl diethylthiolcarbamate, and

have no hydrogen attached to the nitrogen of the thiolallyl dimethylthiolcarbamate; carbamate nucleus. Aromatic radicals are in general less In another experiment sterilized soil was infested with desirable than aliphatic radicals but one phenyl radical in nematodes (Meloidogyne sp.) and different portions conjunction with alkyl of one to three carbon atoms or treated with solutions containing concentrations of 0.1% allyl provides useful compounds providing halogen is conand 0.01% by weight of Z-chloroallyl dimethylthiolcartained in both the 2- and 3- positions of the ester radical. bamate. The treated soil was allowed to stand for a week, While two cyclohexyl substituents reduce effectiveness, then two week old tomato plants were transplanted in the one cyclohexyl in conjunction with an alkyl radical of one test soil and also in untreated, heat-sterilized soil. The to three carbon artoms or allyl comprise a preferred plants were allowed to grow for two months, then were group. Aralkyl groups, as for example benzyl, are suitable harvested, the roots Washed and examined for evidence but not more than one radical should be selected from this of infection. Comparison to the untreated controls gave type. Other unsaturated radicals are suitable especially in the phytotoxicity of the compound. The results showed conjunction with lower acyclic hydrocarbon radicals, as no nematode infestation and no phytotoxicity in both the for example cyclohexenyl and halogen-substituted alkenyl. untreated and treated soils. More than one halogen-substituted radical is usually not The nematocidal compositions attack the soil phase of beneficial. In other words, the presence of a second radithe life cycle of nematode parasites which infest animals.

cal of this type on the nitrogen does not usually increase effectiveness. R in the general formula above includes 4 phenyl piperazinyl.

Controlling harmful and unwanted parasites present in the soil, such as nematodes, is an important problem of considerable complexity. Some of the new compounds are effective for this purpose, notably halogen-substituted alkenyl esters of dimethylthiolcarbamate, as for example 2- chloroallyl and 2,3-dichloroallyl dimethylthiolcarbamate. In order to be an effective toxicant, a compound must be able to penetrate the normally impervious outer covering of the worm as well as the enclosing membranes of the larvae and eggs and to interfere with some vital function of the organism. While the exact mechanism of destroying the soil worm life is not fully understood, it is believed that the effective toxicants destroy or reduce to a low level the effectiveness of vital enzymes. A compound which is effective must be one that will remain in the soil in contact with the undesirable worm life for a sufficient period of time to effect the penetration of the worm and Treating barnyards, chicken pens, stables, and other infested areas destroys eggs and infective larvae of many parasite-s which infest animals. Moreover, the compositions are effective for the control of nematodes in their environment which includes bodies of animals. They are toxic to other worms such as flukes and tapeworms.

In the use of 2-chloroallyl dimethylthiolcarbamate as a nematocide or soil fumigant, the active compound, diluted or undiluted, may be applied to the soil at rates of 10 to 500 pounds per acre. The preferred application for treating soils of average nematode infestation will be from 25 to pounds per acre. Formulation may contain dispersants which aid uniform distribution.

The new compounds are also useful for preventing tarnish of worn silverplate. Synthetic detergents used for hand dishwashing require a tarnish inhibitor. Otherwise, utensils with worn silverplate will acquire a dark brown tarnish.

Tarnish inhibition was demonstrated by the following procedure: Specimens of German silver (nickel silver) were polished with crocus cloth until all stains had been removed and the surfaces were bright and smooth. The method of J. C. Harris et al., A.S.T.M. Bulletin No. 204, February 1955, page 32, was followed for degrasing, claning, and storage of specimens. Stock solutions of the detergents and inhibitors were mixed and diluted to the specified concentrations. Each metal specimen was placed in a 100 ml. beaker containing 50 ml. of detergent and inhibitor soltuion. A control containing no inhibitor was observed for tarnish and discoloration.

The tests were carried out employing as the detergent ammonium dodecylbenzenesulfonate at 0.1% concentration. After 24 hours observations were made as to the presence or absence of tarnish. In the table are recorded observations made in which 2-chloroallyl dimethylthiolcarbamate was employed as the inhibitor:

TABLE VII Concentration percent of detergent solids:

Observation after 24 hours None Visible tarnish. 0.2 No visible tarnish. 0.1 do.

R("3-SR' where R is an organic amino substituent of 2 to 18 carbon atoms, inclusive, having a nitrogen atom directly connected to the carbonyl radical and to two other carbon atoms and is selected from the group consisting of saturated monoaminohydrocarbon of 2 to 8 carbon atoms, inclusive, morpholino, 4-phenyl-1-piperazinyl, disubstituted amino in which the two substituents are selected from the same member of the group consisting of hydrocarbonoxyloweralkyl in which any unsaturation is aromatic, lower-2-alkenyl, and chlorolower-2-alkenyl containing less than three chlorine atoms and having all the chlorine attached to unsaturated carbon, disubstituted amino where one'substituent is selected from the group consisting of lower-Z-alkenyl chlorolower-Z-alkenyl containing less than three chlorine atoms having all the chlorine attached to unsaturated carbon, monocyanoloweralkyl, hydrocarbonoxyloweralkyl in which any unsaturation is aromatic, phenyl, benzyl, and cyclohexenyl, and the other is a different member selected from a group consisting of loweralkyl and hydrocarbonoxyloweralkyl in which any unsaturation is aromatic and R is selected from the group consisting of lower alkenyl, halogen-substituted lower alkenyl having all the halogen attached to unsaturated carbon, and cyclohexenyl. 2. A compound of the structure where R represents a saturated organic monoaminohydrocarbon substituent of 2 to 8 carbon atoms, inclusive, having the nitrogen atom directly connected to the carbonyl group and to two other carbon atoms and R is halogensubstituted lower alkenyl, all the halogen being attached to unsaturated carbon.

3. A compound of the structure Rs N where R is the allyl radical and R and. R are selected from the group consisting of allyl radicals, monochloroallyl radicals and lower alkyl radicals.

6. A compound of the structure n R1-SCN/ where R is a monochoroallyl radical and R and R are selected from the group consisting of-allyl and lower alkyl radicals.

7. A compound of the structure N l S R- where R and R are lower alkyl and R" is 2-cyclohexenyl.

8. A compound of the structure NCSR where R and R are lower alkyl and R is dihalogen-substituted lower alkenyl, all the halogen being attached to unsaturated carbon.

11. A compound of the structure where R and R are lower-2-alkenyl and R" is dihalogensubstituted lower alkenyl, all the halogen being attached to unsaturated carbon.

19 12. A compound of the structure NCSR" where R and R are lower alkyl and R" is chlorine-substituted lower alkenyl containing less than three chlorine atoms, all the chlorine being attached to unsaturated carbon.

13. A compound of the structure N-CSR R! where R and R are lower alkyl and R" is bromine-substituted lower alkenyl containing less than three bromine atoms, all the bromine being attached to unsaturated carbon.

14. A compound of the structure NCSR where R and R are lower alkyl and R" is monochloromonofluoro-lower alkenyl, all the halogen being attached to unsaturated carbon.

. 2,3-dichloroallyl diethylthiolcarbamate. 2-chloroallyl diethylthiolcarbamate. 3,3-dichloroallyl diethylthiolcarbamate. 2-chloroallyl dimethylthiolcarbamate. 2,3-dichloroal1yl diisopropylthiol-carbamate. 2-chloroallyl dipropylthiolcarbamate. Z-bromoallyl diethylthiolcarbamate. The compound methallyl diethylthiolcarbam ate. A thiolcarbamate of the structure where R represents an organic amino radical having a nitrogen atom directly connected to the carbonyl radical and selected from the group consisting of five-membered heterocyclic monoamino hydrocarbon radicals; six-membered heterocyclic monoamino hydrocarbon radicals, morpholinyl; 1,4-piperazinyl, 4-phenyl piperazinyl, hexamethyleneimino,

RI! where R" and R are selected from the group consisting of lower alkyl, lower 2-alkenyl, lower alkoxy-lower alkyl, benzyloxy-lower alkyl, phenoxy lower alkyl and cyanolower alkyl,

Riv

Rv where R is selected from the group consisting of cyclopentyl, cyclohexyl, methylcyclohexyl, cyclohexenyl, cyclooctyl, and phenyl, and R is selected from the group consisting of alkyl of 1-3 carbon atoms inclusive and allyl,

Rvi

4 Evil where R" is selected from the group consisting of chlorolower 2-alkenyl, tetrahydrofurfuryl, furfuryl, octyl and dodecyl, and R is lower alkyl, R represents lower mono-olefinic containing more than two halogen substituents, all of which halogen is attached to unsaturated carbon, halogen being contained in both the 2- and 3- positions when R is phenyl and n is an integer equal to the valence of R.

28 24. A thiolcarbamate of the structure 3 RCSR' where R is heterocyclic monoamino hydrocarbon containing at least five but not more than seven ring members having a nitrogen atom attached directly to the carbonyl group, the hydrogen portion of R containing less than nine carbon atoms and R represents lower monoolefinic having three halogen substituents attached to unsaturated carbon.

25. A thiolcarbamate of the structure R 0 ll N-C where R and R" are lower alkenyl and R represents trihalogen lower 2-alkenyl radical, the halogen being attached to unsaturated carbon.

26. A thiolcarbamate of the structure where R represents an organic amino radical having a nitrogen atom directly connected to the carbonyl radical and selected from the group consisting of five-membered heterocyclic monoamino hydrocarbon radicals;

six-membered heterocyclic monoamino hydrocarbon radicals;

morpholinyl;

1,4-piperazinyl;

hexamethyleneimino;

4-phenyl piperazinyl;

where R" and R" are selected from the group consisting of lower alkyl, lower 2-alkenyl, lower alkoxylower alkyl, benzyloxy-lower alkyl, phenoxy-lower alkyl and cyano-lower alkyl;

Riv

where R is selectel from the group consisting of cyclopentyl, cyclohexyl, methylcyclohexyl, cyclohexenyl, cyclooctyl, and phenyl, and R is selected from the group consisting of alkyl of 1-3 carbon atoms, inclusive, and allyl;

Rvi

Rvii

21 where R' is selected from the group consisting of chloro-lower 2-alkenyl, tetrahydrofurfuryl, furfuryl, octyl and dodecyl, and R is lower alkyl; R' represents trihalogenated lower m0no-2-olefinic, all of which halogen is attached to unsaturated carbon n is an integer equal to the valence of R. 31. A thiolcarbamate of the structure R O II N-O where R is furfuryl, R" is lower alkyl, and R' is trichlorolower m0n0-2-0lefinic, all of which chlorine is attached to unsaturated carbon.

32. A thiolcarbamate of the structure N( SR where R and R" are lower alkyl and R' represents trihalogen lower alkenyl, the halogen being attached to unsaturated carbon.

,33. A thiolcarbamate of the structure where n is an integer at least four but not more than six and R is trichloro lower mono-Z-olefinic, all of which chlorine is attached to unsaturated carbon.

34. 2,3,3-tr-ichloroallyl di(l0wer valkyl) thiolcarbamate.

References Cited UNITED STATES PATENTS 0 ALEX MAZEL, Primary Examiner.

JAMES O. THOMAS, JR., Examiner.

A. ROLLINS, Assistant Examiner. 

1. A COMPOUND OF THE STRUCTURE 